2.

4 Adsorption of phenols

Since 1860, phenol has been in production, with its basic use as an antiseptic. During late 19th
century and thereafter the use of phenol has been further extended to the synthesis of dyes,
aspirin, plastics, pharmaceuticals, petrochemical and pesticide chemical industries. In fact, by
2001, the global phenol production has reached an impressive 7.8 million tons.[19] Among the
different organic pollutants in wastewater, phenols are considered as priority pollutants since
they are harmful to plants, animals and human, even at low concentrations. The major sources of
phenolic are steel mills, petroleum refineries, pharmaceuticals,petrochemical, coke oven plants,
paints,coal gas, synthetic resins, plywood industries and mine discharge. The wastewater with
the highest concentration of phenol (>1000 mg/L) is typically generated from coke processing.
Phonolic compounds are also emanated from resin plants with a concentration range of 12–300
mg/L. Environmental Protection Agency (EPA) has set a limit of 0.1 mg/L of phenol in
wastewater. The World Health Organization (WHO) is stricter on phenol regulation. It sets a
0.001 mg/L as the limit of phenol concentration in potable water. Adsorption of phenolic
compounds from aqueous solutions by activated carbon is one of the most investigated of all
liquid-phase applications of carbon adsorbents.[20] Several adsorbents were used treatment
wastewater and removal of phenols. The adsorption isotherms for mono-, di-, and
trichlorophenols from aqueous solutions on wood-based and lignite-based carbons were
investigated. The adsorptive capacity for 2,4-DCP was found to be 502 mg/g and Freundlich
model gave a best fit the experimental data [21]. Zogorski et al.[22] studied the kinetics of
adsorption of phenols on GAC. They observed that 60% to 80% of the adsorption occurs within
the first hour of contact followed by a very slow approach to the final maximum equilibrium
concentration. In another study, the extent of adsorption of 2,4-dichlorophenol was found to be a
function of pH. The presence of surface functional groups also affected the adsorption of phenols
onto activated carbon. The presence of dissolved oxygen on activated carbon increased the
adsorptive capacity for phenolic compounds This increase in adsorptive capacity was attributed
to the oligomerization of the compounds through oxidative coupling reactions [23]. Hamdaouia
et al. [24] studied and modeled the adsorption equilibrium isotherms of five phenolic compounds
from aqueous solutions onto GAC. The five compounds selected were Phenol (Ph), 2-
chlorophenol (2-CP), 4-chlorophenol (4-CP), 2,4-dichlorophenol (DCP), and 2,4,6-
trichlorophenol (TCP). They also observed that the interaction of phenolic compounds with
activated carbon surface occurred in localized monolayer adsorption type, i.e. adsorbed
molecules are adsorbed at definite, localized sites. Uptake of phenols increased in the order Ph <
2-CP < 4- CP < DCP < TCP, which correlated well with respective increase in molecular weight,
cross-sectional area, and hydrophobicity and decrease in solubility and pKa. Sawdust, a very low
cost adsorbent was used, after carbonization, for the removal of phenol from industrial waste
waters. The equilibrium adsorption level was determined as a function of the solution pH,
temperature, contact time, adsorbent dose and the initial concentration. The adsorption maximum
for phenol using sawdust was 10.29 mg/L.[25] Adsorbents, carbonaceous materials, activated
carbon (AC), bagasse ash (BA) and wood charcoal (WC), were used for removal of phenol from
water.[26]The results showed the removal efficiencies for phenol–AC, phenol–WC and phenol–
BA, approximately 98%, 90% and 90%, respectively. Removal efficiency of phenol slightly
increased when the pH of adsorption system decreased. Yapar and Yilmar.[27] reported the
adsorptive capacity of some clays and natural zeolite materials found in Turkey for the removal
of phenol. They found that calcined hydrotalcite was the best among the studied adsorbents in
which adsorbed 52% of phenol from a solution of 1000 mg/L phenol at the adsorbent/phenol
ratio of 1:100 while the others adsorbed only 8% of phenol. Also, silica gel, activated alumina,
AC, fitrasorb 400 and Hisir 1000 adsorbent were examined as adsorbents for the removal of
phenol from aqueous solution. They found that Hisir 1000 was the best among the tested
materials [28]. Das and Patnaik utilized blast furnace flue dust (BFD) and slag to investigate [29]
phenol adsorption through batch experiment. Bromophenols (2-bromophenol, 4-bromophenol
and 2, 4- dibromophenol) considered as one of toxic organic phenol. Industrial wastes was used
as low cost adsorbent for the removal of these pollutants .

2.5 Batch adsorption parameters

Adsorption processes for decontamination of wastewaters can be carried out either
discontinuously in batch reactors or continuously in fixed-bed reactors or
columns[110,111,112,113] Batch methods are also widelyused because this technology is cheap
and simple to operate and, consequently often favored for small and medium size process
applications using simple and readily available mixing tank equipment. Simplicity, well-
established experimental methods, and easily interpretable results are some of the main reasons
frequently evoked for the extensive use of these methods. Another interesting advantage is the
fact that, in batch systems, the parameters of the solution/ effluent such as contact time, pH,
strength ionic, temperature, etc. can be controlled and/or adjusted
2.5.1 Effect of initial pH on adsorption effectiveness
pH of the solution is one of the most critical parameters that affect the chemical properties of
absorbing and adsorbing .[30]. The solution pH would affect both aqueous chemistry and surface
binding sites of the adsorbent [31]. pH also affects the surface properties of the sorbent, i.e.,
surface charge of the cells used as sorbent [32,33] observed that the adsorption of phenol
decreases by the increase of the pH value of the solution, which can be attributed to the phenol
ionization to form phenolate ions and at the same time the presence of hydroxyl ions on the
adsorbent prevents the uptake of phenolate ions [34]. Similar trend has been reported during the
adsorption of phenol onto bentonite [35,36] defined the phenol removal by Activated carbon
derived from rattan sawdust (ACR) was maximum and unaffected when the initial pH of the
phenol solution was in the range of 3-8. A similar trend of pH effect was observed for the
adsorption of phenol on activated carbon-commercial grade and laboratory grade [37].
Generally, solution pH affects the surface charge of adsorbent and degree of ionization of the
adsorbate [38]. Similar result was given [39] for granule and spherical activated carbon. They
reported that, the decrease in phenol adsorption from pH = 6.3 to 3.07 was due to the increased
H+ adsorption on the carbonyl sites, which suppresses phenol adsorption on these sites [40].
Similar trend has been reported during the adsorption of phenol onto activated carbon [41], onto
rise husk [42] and onto agriculture waste [43,44]. concluded that adsorption amount decreased
with increasing pH value, which can be attributed to the phenol ionization to form phenolate ions
and at the same time the presence of hydroxyl ions on the adsorbent prevents the uptake of
phenolate ions [45]. Similar behavior has been reported during the adsorption of phenol onto
tendu leaf refuse and modified carbon prepared from tendu leaf refuse by[46].
2.5.2 Effect of adsorbent dose on the phenol removal by adsorption process
Because adsorption is mainly a surface phenomenon, the amount of surface available for
adsorption process and consequently the mass of adsorbent can considerably affect adsorption
efficiency [47]. In the investigation which was done by [48] carbon dosage was varied from 0.5
to 10 g and equilibrated for 24 h. It is evident that for the quantitative removal of 25 mg l-1 of
phenol in 100 ml, a minimum carbon dosage of 2.5 g RSCC and 3.0 g of CAC is required for
96% removal of phenol. The data clearly showed that the RSCC is more effective than CAC for
the removal of phenol. [49] indicated that phenol removal increased quickly from 52% to 85%
when the olive mill waste dosage increased from 0.25 g to 1 g and reached a maximum for 1 g
olive mill waste. This trend is expected because as the adsorbent dose increases, the number of
active sites for binding phenol molecules on the adsorbent increases and thus more phenol was
attached to their surface. Thus it results in the increment of adsorption efficiency until saturation.
These results were agreed with those abstained by [50,51]. The minimum adsorbent dosage
required was found by [52], they were 0.3, 0.35, and 0.4 g by BGH, GGH, and RH, respectively.
Thus, the adsorption trend of these agro based adsorbents was found to be in the following order:
BGH>GGH>RH [53,54] work indicated that the increase in phenol removal with increase in the
activated red mud amount is due to the increase of surface area and adsorption sites available for
adsorption [55,56,57].Similar observations have also been reported from other research groups
[58,59,60,61,62,63].
2.5.3 Effect of contact time on the phenol removal by adsorption process
The contact time between adsorbate and adsorbent is one of the most important design
parameters that affect the performance of adsorption processes [64,65]. The removal efficiency
increased with time and attained equilibrium in 3 h for PSCC and 6 h for CAC for initial phenol
concentration of 25 mg l-1 In investigation on removal of phenol from aqueous solutions by
activated red mud which has investigated by [66], while increasing the phenol concentration
from 40 to 80 mg l-1, the removal percentage decreased from 90.3% to 76.6% at initial 30 min of
contact time. After that, the removal percentage of phenol slowly increased and ranged from
90.4% to 80.6% at three different phenol concentrations after 60 min. Further increase in the
contact time has a negligible effect on the rate of phenol adsorption, and 60 min was determined
as a near equilibration time [67]. The decrease in the removal percentage of phenol by increasing
initial phenol concentration can be explained in that the adsorbent had a limited number of active
sites, which can be easily saturated at higher adsorbate concentration [68,69,70,71]. The results
in [72] research showed that equilibrium time required for the adsorption of phenol on wheat
husk was almost 5hr. The results also indicated that the sorption process can be considered very
fast because of the largest amount of phenol attached to the sorbent within the first 120 min of
adsorption as also observed by [73,74,75]. In addition similar findings were reported by other
researchers about the increase of removal efficiency of pollutants with increase of contact time
[76,77]
2.5.4 Effect of initial phenol concentration on the effectiveness of adsorption process
The initial concentration of pollutant provides an important driving force to overcome all mass
transfer resistance of the adsorbate between the aqueous and solid phases [78,79] observed that
phenol adsorption rate by Moringa peregrina tree shell ash will be increased by phenol
concentration, so phenol elimination depends on its concentration. The results in [80] research
indicated that the percentage of phenol removal increases with increasing the adsorbent dose.
The high sorption at the initial concentration (100-500 mg l-1) may be due to an increased
number of vacant sites on the adsorbent available at the initial stage. As concentration of initial
phenol is increased there is a decrease in percentage removal of phenol. This can be attributed to
the accumulation of phenol particles on the surface of adsorbent [81] This observation is in a
good agreement with the findings of [82,83].

2.5.5 Effect of temperature on phenol removal by adsorption process

Temperature is an indicator for the adsorption nature whether it is an exothermic or endothermic
process. Increasing temperature may decrease the adsorptive forces between the phenol species
and the active sites on the adsorbent surface as a result of decreasing adsorption efficiency
[84,85]. [86] concluded that the uptake of phenol by organo bentonite decreased from 6.2 mg g-
1 (59% removal) to 5.2 mg g-1 (49.5% removal) when increasing the temperature from 0 to 40
̊C, which indicating that phenol uptake was favored at lower temperatures. The decrease in
adsorption with the rise of temperature may be due to the weakening of adsorptive forces
between the active sites of the adsorbent and adsorbate species and also between the vicinal
molecules of the adsorbed phase [87,88]. Similar results were obtained by [89] with adsorption
of 2, 4, 6-trichlorophenol by activated clay.

2.6 Adsorption isotherms and models

An adsorption isotherm is the presentation of the amount of solute adsorbed per unit weight of
adsorbent as a function of the equilibrium concentration in the bulk solution at constant
temperature. Langmuir and Freundlich adsorption isotherms are commonly used for the
description of adsorption data. The Langmuir equation is expressed as:
/ 1/ / , Ce qe bXm Ce Xm = + (2)
Where Ce is the equilibrium concentration of solute (mmol L−1), qe is the amount of solute
adsorbed per unit weight of adsorbent (mmol g−1 of clay), Xm is the adsorption capacity (mmol
g−1), or monolayer capacity, and b is a constant (L mmol−1 ). The Freundlich isotherm
describes heterogeneous surface adsorption. The energy distribution for adsorptive sites (in
Freundlich isotherm) follows an exponential type function which is close to the real situation.
The rate of adsorption/desorption varies with the strength of the energy at the adsorptive sites.
The Freundlich equation is expressed as:
1/ , logqe logk nlogCe = + (3)
Where k (mmol g−1) and 1/n are the constant characteristics of the system [90].

2.7 Thermodynamic parameters in the adsorption process

Thermodynamic parameters are the actual indicators to determine where a process proceeds
spontaneously and to ascertain if the process has any practical use [91]. The thermodynamic
parameters that must be considered to determine the adsorption processes are the changes in
standard enthalpy (ΔH0), standard entropy (ΔS0), and standard free energy (ΔG0) due to transfer
of unit mole of solute from solution onto the solid–liquid interface [92]. Adsorption process can
be classified as physical adsorption and chemisorption by the magnitude of the enthalpy change.
It is accepted that if magnitude of enthalpy change is lesser than 84 kJ mol-1, then the adsorption
is physical. However chemisorption takes place in the range of 84-420 kJ mol-1[93,94]. Also If
the process is endothermic (ΔH >0), the equilibrium constant increases with temperature and If
the process is exothermic (ΔH <0), the equilibrium constant decreases as temperature is raised
[95]. The thermodynamic parameters are presented in Table 2. [96] reported that the standard
Gibbs free energies (ΔG0) of adsorption were negative at all investigated temperatures. The
negative values of ΔG0 of the adsorption confirmed that the adsorption of phenol onto LC was
feasible and spontaneous [97,98]. Similar results were reported in the literature for the adsorption
of phenol by organomontmorillonit [99]. and adsorption of phenol onto chemically modified
activated carbon [100]. and adsorption of phenol onto solid waste products from olive oil
industry [101]. [102] reported that the Negative ΔG0 values are obtained at all temperatures
revealing the spontaneous nature of these adsorptions. Generally, the values are close to each
other indicating that such spontaneity is independent on the temperature where the adsorption
occurs [103]. It is also supposed that the change of ΔS0 value is related to the displacement of
the adsorbed water molecules by the adsorbate [104]. In this study, the negative ΔS0 value may
reveal that zeolite surface does not prefer phenol molecules over adsorbed water molecules.
Thus, the adsorption of phenol onto zeolite under employed conditions is considered as an
enthalpy driven process [105].